双锂试剂与6, 6-二烷基富烯的反应-取代茂钛，锆有机化合物的合成

研究了双锂试剂与6, 6-二烷基富烯反应的立体、结构效应。1, 4-丁基二锂、1, 6-己基二锂同6, 6-二甲基、6-甲基-6-乙基、6-甲基-6-正丙基和6, 6-五甲基富烯发生加成反应。对苯基二锂与6, 6-二甲基、6-甲基-6-乙基、6-甲基-6-正丁基和6, 6-四甲基、五甲基、六甲基富烯均进行α-攫氢反应, 但使6-甲基-6-正丙基富烯还原偶联。1, 2, 3, 4-四苯基-1, 4-二锂丁二烯-1, 3同6-甲基-6-正丙基、6, 6-五甲基富烯发生α-攫氢反应。讨论了上述反应的机理。由上述形成的取代环戊二烯基阴离子同CpTiCl~3, (CpTiCl~2)~2O, TiCl~4和ZrCl~4反应, 制得亚甲基桥联和烯基茂钛、锆化合物。

Reactions between dilithium-organo reagent and 6, 6-dialkylfulvenes-syntheses of substituted titanocene and zirconocenes derivatives

The steric structure effect of 6,6-dialkylfulvenes in reaction with 1,4-dilithiobutene (L-A), 1,6-dilithiohexane (L-B), 1,4-dilithiobenzene (L-C) and 1,2,3,4-teoraphenyl-1,4-dilithio-1,8-butadiene (L-D) are studied. Dilithium reagents L-A and L-B adds on the exo-cyclic double bound on 6,6-dimethyl-, 6-methyl-6-ethyl-, 6-methyl-6-n-propylfulvenes and 6,6-pentamethylenefulvene. The a-hydrogen abstraction reaction takes place when dilithium reagent L-C reacts with 6,6-dimethyl-, 6-methyl-6-ethyl-, 6-methyl-6-n-butylfulvenes and 6,6-tetramethylene-, 6,6-pentamethylene-, 6,6-hexamethylenefulvenes, except that the 6-methyl-6-n-propylfulvene undergoes reductive coupling reaction. With larger steric dilithium reagent L-D 6-methyl-6-n-propyl-, 6,6-pentamethylenefulvenes give rise to a-hydrogen abstraction reaction. Besides, a series of methylene-bridged and alkenyl substituted titanocenes and zirconocenes derivatives are prepared